Catalytic hydrogenation of nonnitrogenous organic compounds



Patented Got. 24, 1933 CATALYTIC HYDROGENATION- OF NON- NITROGENOUS ORGANIC COMPOUNDS Alphons O. Jaeger, Crafton, Pa., assignor to The Selden Company, Pittsburgh, Pa., a corporation of Delaware No Drawing. Application February 25,v 1928 Serial No. 256,917

This invention relates to the catalytic hydrogenation of non-nitrogenous organic compounds in the liquid or vapor phase, with orwithout pressure, at ordinary or elevated temperatures.

- According to the present invention non-nitrogenous organic compounds are hydrogenated in the presence of a new class of catalyst compositions, either in the liquid or the vapor phase, by

means of reducing gases of all kinds, for example,

1-O hydrogen, gases containing hydrogen, gases containing carbon monoxide, such as water gas with or without the presence of ethylene, methane,

carbon dioxide, water vapors, nitrogen and the like. In fact any'of the ordinary reducing gases may be used. Contact masses used in the present invention contain base exchange bodies or their derivatives in which at least one component is present in non-exchangeable form or imbedded as a diluent. The invention does not include contact masses containing, when freshly prepared,

base exchange bodies in which the only catalytically active component having specific activity is present in exchangeable form.

Under the term base exchange body are ineluded all natural or artificial bodies which possess the properties of exchanging their bases for other bases of salt solutions. The base exchanging products used in making catalytic compositions of the present invention or as initial material for derivatives to be so used may possess high base exchanging power or in many cases may possess lower base exchanging power, since the catalytic value of the final compositions is not primarily dependent on the amount'of base exchanging power present. Ingeneral the base exchange bodies may be divided into three main categories:Two component and multi-component zeolites, i. e., base exchange bodies containing chemically combined silicon in their nucleus and non-silicious base exchange bodies in which all of the silicon is replaced by other'suitable acidic or amphoteric metal oxides. Twocornponent zeolites are the reaction products of two typesof initial components, that is to say, metallates and silicates, (using the term metallate in a somewhat broader sense as will be defined further on in the description), or metai salts and silicates. Frequently more than one member of a type may enter into reaction, that is to say, a silicate may react with more than one metallate or more than one metal salt. The multi-component zeolites are the reaction prodnets of at least three types of components, that is to say, at least one silicate, at least one metallate, and at least one metal salt.

The base exchange bodies, both zeolites and non-silicious base exchange bodies, may be associated with diluents preferably in the form of a physically homogeneous structure, as will be described below. Either diluted or undiluted base exchange bodies may be present in the contact masses used in the present invention, or their derivatives may be present, but it should be understood that wherever base exchange bodies are referred toboth diluted and undiluted products 65. are included.

Base exchange bodies, both zeolites and nonsilicious base exchange bodies, may also be transformed into derivatives which possess many of the chemical and most of the physical characteristics of the parent base exchange bodies. Such derivatives may be salt-like bodies, that is to say, the reaction products of base exchange bodies with compounds containing anionscapable ofreacting with the base exchange bodiesto form products which possess many of the propertiesof salts. A further class of derivatives are the acid leached base exchange'bodies. .When a base exchange body is subjected to leaching by acids, particularly dilute mineral acids, the exchangeable bases are first gradually removed. The, resulting products contain both the more basic and the more acidic components of the non-exchangeable nucleus of the base exchangebody, with or without a portion Off/he exchangeable bases. As the leaching is carried on further, more and more of the relatively positive components of the nonexchangeable nucleus are removed, and ifcarriedtocompletion the leached product contains only the relatively acid components of the nonexchangeable nucleus. In the case of zeolites the final product from long continued leaching is a complex silicic acid which has many of the physical properties of the original base exchange body. In the description and-claims the class of base exchange bodies and their derivatives will be referred to by the generic term permutogenetic products.

Catalytically active components may be associated with diluted or undiluted permutogenetic bodies in three main forms as follows:--( 1) They may be physically admixed with or impregnated into the permutogenetic products. (2) They may be physically homogeneously incorporated into the permutogenetic products before the latter have been completely formed in the, form of catalytically active diluent bodies or in the form of diluents which have been impregnated with catal-ytically active substances. (3) They may be chemically combined with or in the permutogeno netic products in non-exchangeable form, that is to say, they may form a part of the non-exchangeable nucleus of the base exchange body present in the final contact mass or which is transformed into the derivatives, or they may be chemically combined with the base exchange bodies in the form of catalytically active anions which form with the base exchange body salt-like bodies. Obviously of course the same or diiierent catalytically active components may be present in more than one of the above described forms, and it is an advantage of the present invention that catalytically active substances may be chemically combined in non-exchangeable form or physically combined with permutogenetic bodies in a wide variety of forms, which gives a wide field of choice to the catalytic chemist. While the differ ent permutogenetic products may vary widely in their chemical characteristics, they all possess a similar physical structure which is characterized by more or less high porosity, frequently microporosity, and great resistance to high temperatures, and in the case of products which have not been acid leached to the point of removal of catalytically active components these components are distributed throughout the framework or" the products in atomic or molecular dispersion, as'will be described in greater detail below, and this chemical homogeneity is one of the important advantages of some of the contact masses of the present invention.

While two of the methods of combination of the catalytically active substances may be effected with undiluted as well as diluted permutogenetic products, it has been found that for most reactions homogeneously diluted permutogenetic contact masses are of advantage, particularly where the diluents are of a physical nature such as to exert a desired influence on a catalytic activity of the contact masses, as when, for example, diluents are rich in silica, which has been found to have an activating power, or where the diluents by reason of high porosity, capillarity, or surface energy maybe considered as physical catalysts or activators.

Base exchange bodies used in contact masses of the present invention behave as if they were products of extremely high molecular weight for catalytically active components can be introduced either into the non-exchangeable nucleus in practically any desirable proportions and the ordinary law of chemical combining proportions, which in compounds of low molecular weight restricts the proportions in which components can be incorporated chemically, appears to be without force, which makes it reasonable to assume that the molecular weight is so high as to completely mask the effect or" the law. It is of course pos sible that the base exchange bodies, or some of them, may be solid solutions of a. plurality of related compounds of lower molecular weight. It has not been possible hitherto to definitely settle this question, as base exchange bodies are not readily capable oi structural chemical analysis. The present invention is of course not limited to any theory, but irrespective of the underlying reasons the fact that-catalytically active components may be chemically introduced in any desired proportions is of enormous importance to the catalytic chemist and gives him the power to produce an almost unlimited number of finely and gradually toned catalysts or contact masses for the various reductions and hydrogenations of non-nitrogenous organic compounds. In all cases the contact masses produced are highly effective by reason of the desirable physical structure of the permutogenetic products contained therein and the wide limits of homogeneous dilution of catalytically active molecules or atoms with resulting uniformity and smoothness of action, which is of great importance, particularly for some relatively sensitive hydrogenations in cluded within the scope of the present invention. In addition to the important characteristics with which permutogenetic products endow the contact masses of the present invention it has been found that for many of the reactions coming within the scope of the present invention it is desirable to stabilize the contact masses, and this may be effected by associating with the per mutogenetic products or incorporating or forro ing therein compounds of the alkali forming metals, that is to say, alkali metals, the alkaline earth metals, and the strongly basic earth metals. These compounds appear to slow up or smooth out the catalytic reaction, and will be referred to throughout this specification as stabilizers. While for some reactions strongly alkaline stabilizers are not harmful, it has been found that for many reactions it. is important to provide non-alkaline stabilizers, such as for the salts or compounds of alkali forming metals which do not possess an alkaline reaction. It a great advantage of the present invention that in the normal formation of base exchange bodies alkali forming metal oxides are present as exchangeable bases, and whether used without acid treatment or treated with acid, they form stabilizers which are combined in or associated with the "esulting permutogenetic products in an extremely fine state of division in which the stabilizers are peculiarly active. Thus base exchange bodies containing alkali forming metal exchangeable bases may be considered as complex stabilizersl i In addition to the use of stabilizers which are important a large number of hydrogenations included in the scope of the pre ert invention, it has been found that the stabilizer-action and the overall effici ncy of the contact masses can in many cases be greatlyincreased or enhanced with the association therewith or chemical combination therein of elements or radicals or groups which are catalytically active but do not possess specific catalytic activity for the particular reaction to be carried out. Thus for example in the case of a hydrogenation reaction, certain catalysts which at the temperatures used in the reaction behave as dehydrogenation catalysts be added to enhance, and tone the catalytic activity of the catalysts or the operation of the stabilizers. Similarly in some cases oxidation catalysts, such as those containing metal elements of the fifth and sixth groups of the periodic system may greatly improve theeiifectiveness of the contact mass used, especially where it is des able to produce intermediate products which in some cases are relatively unstable. Some other reduction reactions involve thesplitting off of water or in some cases the splitting oi? of carbon dioxide, I

and may also involve molecular condensations. In such reactions it is very desirable to incorporate catalysts or catalytic components which. not specific reduction catalysts but-which may favor dehydration, splitting off of carbon dioxide or condensation. Such catalysts or catalytic components which are not specificcatalysts for the reaction in which they are being used under the reaction conditions obtaining will be referred to, throughout the specification as stabilizer promotors, as they appear to enhance the toning effect which can be achieved by stabilizers. The use of this expression should, however, in no sense be taken to limit the invention to a particular theory of action of these non-specific catalysts and in face in some cases stabilizer promoters may be present where there are no stabilizers.

The tremendous range of chemical groups which may be combined in or with or incorporated in permutogenetic products PETA. its a wide choice of stabilizer promoters as well as specific catalysts andpermits their association with the contact masses in an extremely homogeneous and catalytically eificient form. Thus'many base exchange bodies or their derivatives may be considered as complex catalysts, stabilizers and stabilizer romoters, as all of these elements may be present in the same chemical compound and sharing the advantages flowing from its desirable physical structure and chemical properties. Of

course both stabilizer and stabilizer promoters may be mixed partly or wholly with permutogenetic products and a single stabilizer or single a stabilizer promoter may be present partly in physical admixture and partly in chemical combination, as will be clear to the skilled base exchange chemist.

The base exchange bodies which form the important components or initial material for derivatives in contact masses of the present invention may be prepared in any of the well known meth ods. Thus for example, two-component zeolites may be prepared by wet methods, in which the silicate types, or the components may be fused, io-

metallate com onents or metal salt components,

part or all of which may be catalytically active, are caused to react with soluble silicates to form zeolites of alumino silicate or aluminum double preferably in the presence or" fluxes. It should be understood that under the term metallate is included not only the alkaline solutions of am photeric metal oxides or hydroxides but also alkali forming metal salts of metal acids, such as'the oxyacids of metals of the fifth and sixth groups, which in at least one stage of oxidation are not strictly speaking amphoteric, but which products are capable of reacting with silicates to form zeolites, or with other components to form non-silito litmus are of advantage.

cious base exchange bodies. Throughout the specification this somewhat more general definition or" metallates will be strictly adhered to. In the formation of two-component zeolites by wetmethods, the final reaction product must be alkaline to litmus, and for products of high base exchangin power it should be neutral or alkaline to phenolphthalein. For the purpose of producing base exchange bodies to be used in the preparation of contact masses of the present invention it is sometimes unnecessary to provide high base exchanging power, and for many purposes zeolites formed under conditions resulting in a final reaction which is acid to phenolphthalein but alkaline It is not definitely known whether products produced under such circumstances are homogeneous chemical compounds, although in many ways they behave as such. There is, however, reason to believe that in some cases at least mixtures 01 baseexchanging and non-base exchanging polysilicates may be produced; For the purpose of the present specification a product will be considered as a base exchange product if it has any base exchange power at all. I It is desirable for many purposes and particuin most cases, but the opposite procedure is ad:

vantageous for certain contact masses and is included in the invention.

Multi-component zeolites may be prepared by any or" the foregoing methods using at least three types of components, that is to say, at least one inetallate, at least one metal salt and at least one soluble silicate. In the case of multi-component zeolites, as in the case of two-component zeolites, the conditions of alkalinity should be observed, and for many purposes it is advantageous to add the relatively acid components to the relatively alkaline components, in order to insure continuous alkaline reaction. The multicomponent zeolites produced vary in their nature, dependent on the proportion of the diiierent reacting components. Thus where the metallates and silicates predominate over the metal salts the resulting products-resemble the alumino silicate type of two-component zeolites. If the metal salts and silicates predominate over the metallates the products resemble the aluminum double silicate type of two-component zeolites, and finally i the metallates and metal salts predominate the silicates the resulting product resembles more or less non-silicious base exchange bodies.

It will be clear tbat there is no sharp defining line between the three types of inulti-component zeolites, and one shades into the other as the proportions of the different components vary. It is an advantage of the multi-component zeolites over the two-component zeolites that the choice or" catalytically ctive components is wider, as some catalytically active elements or groups can only be incorporated in the form of metallates and others only in the form of metal salts. In a multi-component zeolite each catalytically active group can be incorporated in the form in which it is best available.

Nori-siliciousbase exchange bodies are produced by the general methods described above; but instead of bringing about reactions between silicates and other metal oxide components, two or more oxymetal compounds are caused to react, in general, at least one will be a metallate and at least one a metal salt,'or in some cases it is possible to bring about action between two different metallates in which one negative radical is more acidic than the other. It is possible to pro-- duce non-silicious base exchange bodies in which a plurality of metal oxides are present. It is also possible to produce non-silicious base exchange bodies in which a single metal is present. Thus forexample, some metals may be sufiiciently amphoteric in character to form both metallates and metal salts which are capable of reacting with each other to produce-base exchanging bodies.

A special method of producing non-silicious base exchangebodies consists in the gradual neutralization of strongly alkaline salts of the oxyacids of metal elements of the fifth and sixth groups in stages of oxidation in which they are sufiiciently amphoteric. The neutralization of other strongly alkaline metallates may also bring about formation of non-silicious base exchange bodies. The converse method, whereby nonalkaline salts of suitable metals are gradually treated with alkali until the reaction is sufiiciently alkaline to permit the formation of base exchange bodies, may also be used.-

Many metals are capable of entering into the base exchange formation only in certain stages of oxidation, and it is sometimes necessary to introduce such metals in a stage of oxidation different from that desired in the final base exchange body, the change of stage of oxidation being preferably effected. during the formation of the base exchange body. Certain other elements may be incorporated in the form of complex compounds of the most various types, such as for example, ammonia complexes and the like.

In addition to the artifical base exchange bodies briefly described above, natural base exchange bodies, such as nepheline, leucite, felspar, and the like, may be used.

The most important contact masses for many reactions contain permutogenetic products, in which preferably the diluents are homogeneously incorporated into the base exchange bodies before formation of the latter, or at least before the base exchange body has set after formation. Many diluents, both inert, stabilizing, activating, catalytically active, or having stabilizer promoter effects, can be used. A few of the diluents will be briefly enumerated:-kiselguhrs of all kinds particularly natural or treated celite earth, silicious powders of various types, powdered permutogenetic products, natural or artificial powders of rocks, stones, tufis, trass, lava, and similarly volcanic products which are frequently highly porous, greensand, glauconite or its acid leached derivative glaucosil, pulverized slag wool, cements, sand, silica gel, pulverized earthenware, fullers earth, talc, glass powder, pumice meal, asbestos, graphite, activated carbon, quartz meal, various pulverized minerals rich in quartz, metal powders and metal alloy powders, salts of oxy-' metal acids such as tungstates, vanadates, chromates, uranates, manganates, cerates, molybdates, etc., particularly copper salts of the above, silicates, such as copper silicate, iron silicate, nickel silicate, cobalt silicate, aluminum silicate, titanium silicate, minerals or ores, especially those rich in copper, etc. Finely divided diluents are of great advantage, especially when the average particle size is less than to microns, in which case the diluents possess high surface energy, which increases the adsorptive and absorptive capacity of the contact mass, the difiusion speed and porosity. These finely divided diluents may be considered as physical catalysts or activators. Diluted permutogenetic bodies also be finely divided and used as part or all of the diluents or" other base exchange bodies.

The following nine methods are the most effec tive for the introduction of diluents, but any other suitablemethods can be used.

(l) The diluents may be mixed with one or more liquid components of the base exchange bodies to be formed when the latter are prepared by wet methods.

(2) Components, either catalytically active, stabilizer promoters, or others, may be precipitated or impregnated into diluent bodies which are then incorporated into the base exchange bodies by any suitable methods of incorporation.

(3) Diluents may be mixed with base exchange bodies while the latter are still in the form of gels, by kneading or stirring, in which case the base exchange gel behaves as an adhesive. The homogeneity and uniformity of the distribution of the diluents is of course not so great by this method as by method (1), but for many catalytichydrogenations of non-nitrogenous organic compounds extremeuniformity is not essential.

i) Dilucnts may be formed during the formation of base exchange bodies by mixing suitable compounds with the components of the base exchange bodies. so that the diluent particles are precipitated during formation. Protective colloids may be added to prevent coagulation of the diluent particles before the base exchange bodies have become sufliciently set.

(5) Compounds may be added which react with certain of the base exchange body forming components to produce diluents, for instance salts of the metal acids of the fifth and sixth groups may be added in suificient excess so that they react with components of the base exchange body to form insoluble diluents, as for example with heavy metal oxides.

(6) Preformed base exchange bodies, diluted or undiluted, artificial or natural, can be impregnated with true or colloidal solutions or" catalytically efiective components and then dried.

(7) A preformed base exchange body, diluted or undiluted, may impregnated with a plurality of solutions which react therein to precipitate any desired diluents.

(8) Soluble diluent compounds may be added to the components forming base exchange body, which after formation retains the compounds in solution and is dried without washing or is treated to precipitate the compounds.

(9) Natural base exchange bodies or artificial exchange bodies, diluted or undiluted, or th =1: derivatives, may be impregnated with solutions or" the desired compounds, which are then precipitated by "neans or" reactive gases.

The nucleus or non-exchangeable portion of the molecules of the base exchange bodies is ordinarily considered to consist of two types of oxides, namely, relatively basic metal oxides, usually amphoteric, and relatively acidic oxides, such as SiOz, some amphoteric metal oxides and some metal oxides which have a distinctly acid charactor. The nucleus behaves as a single anion and cannot be split by ordinary chemical means, but it is advantageous to consider the two portions of the nucleusas the basic and acidic portions, bearing in mind of course that the nucleus behaves as a single group. The metal compounds which are capable of forr ing'the'basic' portion of the nucleus are those of the following metals:- copper, silver, gold, bismuth, beryllium, zinc, cadmium, boron, aluminum, some rare earths titanium, zirconium, tin, lead, thorium, niobium, antimony, tantalum, chromium, molybdenum, tungsten, uranium, vanadium, manganese, iron, nickel, cobalt, platinum, palladium. Compounds of these elements may be introduced singly or in mixtures, in any desired proportions, and may be in the form of simple or complex ions.

It should be understood that some of the elements in certain stages of oxidation may be introduced either as metallates or metal salts. Others may be introduced only one form, and

still others may be introduced in a stage of oxidation other than that desired in the final base exchange body or in the form of complex compounds. Among the complex ionogens are ammonia, hydrooyanic acid, oxalic acid, formic acid, tartaric acid, citric acid, glycerine, and the like.

Many of the metals are specific catalysts, others are stabilizers, and still others are stabilizer promoters. Naturally the. status of an element as catalyst or stabilizer promoter will vary with the particular reduction or hydrogenation reaction for which the final contact mass is to be used, and the choice of catalysts and stabilizer promoters together with the proportions will be determined by the particular catalytic reduction or hydrogenation of the particular organic compound forwhi h the contact mass is to be used.

Examples oi'oomponents forming the relatively acid portion of the base exchange nucleus" are alkali metal silicates, which. are soluble in alkali, and alkali metal salts of acids, such as those of boron, phosphorus, nitrogen, tin, titanium, vanadium, tungsten, chromium, niobium, tantalum, uranium, antimony, manganese, etc.

The exchangeable bases of the base exchange bodies may be substituted by base exchange, and the elements which can be introduced singly or in admixture by base exchange arethe follow-V ing:-copper, silver, gold, ammonia, beryllium, calcium, manganese, caesium, potassium, sodium, zinc, strontium, cadmium, barium, lead, aluminum, scandi'um, titanium, zirconium, tin, anti mony, thorium, vanadium, lithium, rubidium, thallium, bismuth, chromium, uranium, manganese, iron, cobalt, nickel, ruthenium, palladium, platinum and cerium.

Depending on the reactions in which the contact mass is to be used, the exchangeable bases introduced may be specific catalysts, they may be stabilizers, or they may be stabilizer promoters. They may be introduced as simple ions or as complex ions, and may enhance the catalytic activity of the final contact mass, imorove its physical structure, or both. It should be understood that while the present invention does not include hydrogenations in which permutogenetic contact masses are used containing exchangeable bases as their only specific catalysts certain catalytically active elements such as, for example, some of those enumerated in a foregoing paragraph, may be introduced by base exchange into contact masses which already contain specific catalytically active components present in non-exchangeable form either in the non-exchangeable nucleus of the base exchange molecule or chemically united therewith in the form of anions to produce salt like bodies or imbedded therein in the form of diluents.

As has been described above, base exchange bodies can be caused to react with compounds containing acidic radicals capable of forming therewith salt-like bodies. The radicals may be present in the form of simple acid radicals, polyacid radicals or complex acid radicals, and include radicals containing the following elements:- chromium, vanadium, tungsten, uranium, molybdenum, manganese, tantalum, niobium, antimony, selenium, tellurium, phosphorus, bismuth, tin, chlorine, platinum, boron. Among the complex radicals are ferro and ferricyanogen, certain ammonia complexes and the like. The amount of acid radicals caused to unite with the base exchange bodies to form salt-like bodies may be varied so that the resulting products may possess the character of acid, neutral or basic salts. Most of these acids radicals are stabilizers or stabilizer promoters for the catalytic hydrogenation of nonnitrogenous compounds. 5 V

The base exchange bodies diluted or undiluted, orsome of their salt like body derivatives, may

be treated with acids, such as mineral acids, for

example 240% sulfuric, hydrochloricor nitric acids, to remove part or all or" the exchangeable bases, or also part or all of the basic portion of A the nucleus.

In the case of zeolites, the partial leaching with acid, which leaves part or all of the basic portion of the nucleus or even part of the exchangeable bases, does not affect the function of the Zeolites as catalysts when they contain cataiytically active elements in the basic portion of the nucleus, or in some cases even exchangeable bases, and such partially leached catalysts are of great importan e in many reactions. Where the leaching is carried out to completion the advantageous physical structure remains to a considerable extent the; same-but the remainder is of coiu'se a form of silica, or in the case of zeolites in which. part of the silicais replaced byother acidic compounds, a mixture or" the two, and usually'will not be a specific catalyst for the hydrogenation of non-nitrogenous organic compounds. It serves, however, as an advantageous physical carrier of specific catalysts, and in the case of partially substituted zeolites may also contain stabilizer. promoters.

Leached non-silicious base exchange bodies, either partially or completely leached, may contain catalytically active components and behave as catalyst, stabilizer promoters or both, and many important catalysts for the hydrogenation of non-nitrogenous organic compounds are thus obtained. This is particularly the case for reactions where a relatively alkali-free contact mass is required for best results and where the alkaline contentof a contact mass containing a base exchange body may be too great for optimum results.

Base exchange bodies or their derivatives, di luted or undiluted, may also be coated in the form of films on massive carrier granules or may be impregnated therein. The massive carriers may be inert, activating, or themselves catalysts. For example, certain catalytic metal alloys, minerals, especially copper minerals, fall within this class. Aluminum or copper alloy granules perform an additional advantageous function in that their relatively high heat conductivity tends to prevent local overheating in highly exothermic hydrogenations of non-nitrogenous organic compounds which is of considerable importance in obtaining good yields, as

many of the reactions, particularly hydrogenations, are equilibrium reactions, and at higher temperatures hydrogenation catalysts reverse their function and tend to favor dehydrogenation with resulting lowering of yields and contamination of the product.

Example 1 into the solutionuntil the mixture just remains i 'stirrable.

A 10% aluminum or zirconium nitrate solution, or a mixture of both, or a corresponding mixture of zirconium and manganesenitrate solutions is prepared. 30 parts of nickel nitrate with 6 mole of water are dissolved in ammonia water to form a dilute nickel ammonium nitrate solution. The nickel salt solution is stirredinto the waterglass suspension and then the aluminum or zirconium nitrate solution is added until the reaction mixture remains only weakly light blue jelly precipitates and on stirring is transformed into readily filterable aggregates. The precipitate is a diluted three-component base exchange body in which the catalytically effective constituents are present in non-exchangeable form or may partly be embedded in the form of diluents. If desired, the mechanical strength of the contact mass may be increased after separating from the mother liquor by washing it with a dilute waterglass solution to effect surface silicification.

If desired all of the catalytically eifective constituents may be embedded in the form of diluents in which case nickel or nickel compounds with or without admixed copper, manganese, cobalt, iron, silver and gold compounds, may be used. All of these compounds are effective hydrogenation catalysts.

The contact mass is reduced with hydrogen or hydrogen-containing gases at 250-320" C. and results in an excellent hydrogenation catalyst. Preferably this preliminary treatment should be carried out in converters having. automatic heat exchange devices in order to closely control the temperature which is an important factor in obtaining contact masses of the highest eifectiveness.

After reduction the contact mass is filled into a converter, preferably provided with means for recirculating the unreacted gases after removal of the reaction products and naphthalene vapors admixed with an excess of hydrogen are passed through the converter at temperatures from 180 to 220 C. A good yield of tetrahydronaphthalene is obtained or by somewhat changing the reaction conditions, such as the gas speed, the reaction may also be carried to decahydronaphthalene. Similarly benzene or homologues or derivatives may be reduced by means of these contact masses. Thus, for example, benzene with a 20-50% excess of hydrogen is passed over the contact mass at 180-220 C. and a good yield of cyclohexane is obtained. At the same temperatures cyclohexanol containing some cyclohexanone as an impurity may be obtained from phenol. The same contact masses may also be used for the catalytic hydrogenation of anthracen and the various stages of tetra-octa-, and decahydroanthracene can be obtained by passing anthracene vapors admixed with hydrogen over the contact mass at zoo-220. The nature of the product obtained will depend to a large extent on the amount of hydrogen used. In a similar manner other aromatic hydrocarbons or compounds can be hydrogenated. Thus, for example, naphthols can be effectively transformed into decahydronaphthols, and phenanthrene can be hydrogenated to useful products.

The use of pressure in these hydrogenation applications is also favorable and when operating under pressures above atmospheric it is usually feasible to carry out the reactions at somewhat lower temperatures. It should be understood that the contact masses described which contain stabilizers in the form of alkali and stabilizer promoters having dehydration, dehydrogenation and oxidation effects permit the hydrogenation of double bonds any of the compounds where they occur and aliphatic as'woll as aromatic compounds may. be effectively hydrogenated.

The contact masses described above can be further improved by introducing stabilizer promoters by base exchange or by embedding further amounts as diluents. In this manner alkaalkaline or neutral to phenolphthalein. A stiff lies, alkaline earth oxides, rare earth oxides, or bases containing cadmium, aluminum, titanium, zirconium, cerium, thorium, vanadium, chromium, or uranium may be introduced singly or in admixture. As an example,'3-5% of calcium chloride, chromium nitrate, magnesium chloride or cadmium nitrate solutions may be employed. Preferably the base exchange is effected by causing the solutions, after warming to ail- (3., to trickle over the base exchange body. The amount of stabilizer or stabilizer promoters thus introduced is not of vital importance. The main feature consists in having a certain amount of them present and in general suificient base exchange can be effected by causing a salt solution containing 500-600 parts to trickle over the base exchange body. Instead of introducing stabilizer promoters by base exchange, active catalysts may also be introduced in this manner and will enhance the catalytic power of the contact masses. Thus, for example a 3-5% solution of nickel nitrate, iron nitrate, cobalt nitratasalts of lead, zinc, or cobalt may be used.

Further amounts of stabilizer promoters may also be introduced by forming the salt-like bodies of the base exchange body wan acid radicals of the metal acids of the 5th and 6th groups of the periodic system, such as, for example, vanadic acid, tantalic acid, bismuthic acid, columbic acid, chromic acid, molybdic acid, tungstic acid, and the like. Preferably, salt-like bodies are formed by impregnating the base-exchange body with ammonium salts of the acids. Dilute solutions may be used and if necessary washing may be resorted to. If heavy metal oxides are present in the base exchangeportion of the molecule the color of the metal acid will appear. For example, vanadic acid may be introduced by trickling a 1% ammonium vanadic solution over a base exchange body followed by washing, if'necessary.

Instead of using the contact masses for hydrogenations in the vapor phase as described above, they may also be used in liquid phase reactions for the hardening of fats, oils and other liquid phase hydrogenations. In such a case, of course, the contact mass is present in suspension and the reaction may be carried out with or without super atmospheric pressure.

Example 2 A contact mass is prepared as follows:

20-30 parts of SiOz in the form of a commercial waterglass solution are diluted with 7-8 volumes of water and kieselguhr, asbestos, or quartz powder is added until the mixture ust remains readily stirrabl A mix d solution i prepared by dissolving 10 p2 of ni kel nitrate with 6 mols of water to a 2N. solution mixing with an aluminum chloride solution of the same concentration containing an amount of aluminum corresponding to 2.5 parts of A1203. he mixed nickel-aluminum salt solution is then added to the waterglass suspension until the reaction product'and the mother liquor react slightly alkaline or neutral to phenolphthalein. The' The contact mass thus 1 i pounds. For example, acetylene mixed with hydrogen may be reduced to ethylene or ethane, depending on the amount. of hydrogen used. When the theoretical amount of hydrogen, that is "to say 2 volumes of hydrogen to one of acetylene, is used and the mixture passed over the contact mass at 140482 C. ethylene is obtained as the main product containing some unchanged acetylene and a small amount of higherhydrocarbons. When an excess of hydrogen is used the main product is ethane, Other olefines may be transformed into saturated hydrocarbons, such as, for example, propylene to propane.

Using the same contact mass the unsaturated side chains of aromatic compounds may be hydrogenated. Thus, for example, styrene may be transformed into ethylybenzene and stiibene can similarly be transformed into dibenzyl. The temperature should be somewhat higher than for the aliphatic hydrogenations, preferably between 220-270" C., and an excess of hydrogen should ordinarily be used.

The effectiveness of the contact mass can be enhanced when small amounts of copper or manganese are present in the non-exchangeable nucleus in addition to the nickel. They may also be present in the form of diluents, thus, for example, the kieselguhr used may be impregnated with 3 parts of cupric hydroxide prepared in the usual manner by first impregnating the kieselguhr with a copper nitrate solution and then precipitating the hydroxide with normal sodium hydroxide, the impregnated kieselguhr being, of course, first dried before introduction into the waterglass solution. A further improvement can be effected by leaching the base exchange body with acid, preferably 2-3% nitric acid in order to leach out part of the exchangeable alkali. After leaching is completed the base exchange body should be dried and reduced with hydrogen containing gases at 300350 C.

Example 3 7 Four solutions are prepared, as follows:

1. 27 parts of freshly precipitated chromium hydroxide in the form of a suspension, as obtained by precipitation from the corresponding chromous salt solution, are treated with sufiicient 2N. sodium hydroxide solution to transform them into the corresponding sodium chromite.

2. 8 parts of cadmium nitrate with 4 mole of water are dissolved in parts of water and sufficient 2N. sodium hydroxide solution is added-until the corresponding sodium cadmiate solution is obtained. I 1 3. 4 parts of V204, freshly prepared by reducing.

a. corresponding amount of V205, are dissolved in 5N. sodium hydroxide solution to the coffee brown sodium vanadite.

i. 50 parts of nickel itrate are dissolved in 250 cadmium, vanadium and nickel in non-exchange- .what elevated temperature.

able form diluted with the finely divided silicious material, or activated carbon. The base exchange body is preferably hydrated with water by trickling the latter over the crushed base exchange fragments, and'then dried, whereupon it is reduced with hydrogen-containing gas at to i-- peratures from 250 to 350 C.

The contact mass prepared as described above is very effective for the catalytic hydrogenation.

of unsaturated alcohols to saturated alcohols, for example allyl alcohol to propyl alcohol; for the hydrogenation of esters of unsaturated acids such as for example the esters of rnaleic and fumaric acids to esters of succinic acid, esters of acrylic acid to esters of propionic acid and the like; for the hydrogenation of unsaturatedethers for example allyl ether to propyl ether; forthe hydrogenation of unsaturated aldehydes such as acrolcin to propionaldehyde, crotonaldehyde to butyraldehyde; for the hydrogenationof unsaturated ketones; for the hydrogenation of unsaturated acids, such as for example maleic acid to succinic acid, crotonic acid to butyric acid, oleic acid to stearic acid, and the like. The hydrogenation should take place in the'presence of hydrogen-containing gases, using either the theoretical amount or, preferably, an excess, and may be carried out either in the vapor phase or in the liquid phase, with or without pressure at ordinary or elevated temperatures.

As an example of these reactions dimethyl maleate, having a boiling point of 205 C., with or without admixture of dimethyl fumarate with a boiling point of 192 'C., is vaporized with a more or less, great excess of hydrogen and passed over the contact massat 170-190 C., preferably in a converter which permits close control of temperature such as a converter provided with automatic double counter current heat exchange. The corresponding dimethyl ester of succinic acid is obtained and if desired may be saponified to produce succinic acid of high purity.

Under the same reaction conditions free maleic 'acid can'also be hydrogenated to succinic acid with an excess of hydrogen, but where any considerable amount of fumaric acid is presentthe latter is not sufliciently volatile to get into the gas stream, and it is therefore preferable in most cases to hydrogenate the esters.

s The same contact mass may be used for hydrogenating these esters or acids in the liquid phase. Instead of using the acids, however, which would strongly corrode the reaction vessel, the alkali metal salts such as the sodium salts, may be used in aqueous solution, the catalyst of course being suspended as in all liquid phase reactions. While the process can becarried out at room temperature, it is preferable to use a some- Instead of using the concentrated esters, they may be diluted with indifferent solvents such as alcohols, acetone, cyclohexane, cyclohexanol and the like. It is. also possible to emulsify the esters'with .waterb ut very vigorous agitation must be maintained in order to keep a good emulsion,

The contact mass may be further modified by introducing copper through base exchange, for example by trickling '3 to 5% copper salt solutions leaching the base exchange catalyst with dilute acid to leach out the exchangeable alkali present, the desirable physical structure of the contact mass being retained. The leached product should be reduced at Silo-408 0., and can then be effectively used for the hydrogenation of unsaturated alcohols, aldehydes or ketones, for example crotonaldehyde may be reduced with gases con- ,taining hydrogen in the theoretical amount or in small excess, the mixture being passed over the contact mass at 120-1&0 C. and producing butyraldenyde as the main product. Some butyl alcohol is obtain d as a by-product.

Example 4 50 parts of kieselguhr are suspended in 300 parts or" water and 50 parts of concentrated hydrochloric acid are poured in and the whole is heated up to GO- ZO" C. with vigorous agitation. The kieselguhr is filtered off and washed with distilled water until entirely free from acid and the purified product is suspended in a nickel nitrate solution containing 130 parts of nickel nitrate with 6 mols of water in 500 c. c. of water. Nickel hydroxide is then precipitated in a fine state of division in the kieselghur using 2N. sodium hydroxide solution, whereupon the mass is filtered and carefully washed with distilled water until free from sodium nitrate.

24 parts of S102 in the form of a commercial sodium waterglass solution, as free from iron as possible, are diluted with 250 parts of water and the kieselguhr impregnated with nickel hydroxide is suspended therein with vigorous agitation.

8 parts of A1203 in the form of the hydroxide freshly precipitated from a salt solution with ammonia are treated with 2N. sodium hydroxide solution until all of the aluminum oxide goes into the solution as sodium aluminate. This solution is then poured into the waterglass suspension with vigorous agitation and heated to 50-60" C. resulting in the precipitation of an aluminum zeolite containing nickel hydroxide and lrieselguhr as diluents. The yield of the zeolite may be increased by neutralizing any excess of alkali with dilute nitric acid. The zeolite is then sucked from the mother liquor, washed with 500 parts of water in small portions and dried preferably at temperatures below 100 C.

After drying the zeolite is hydrated with water in the usual manner, again dried and pulverized and then treated with hydrogen-containing gases. After this preliminary treatment the contact mass is well suited for the catalytic hardening of oils. The effectiveness of the zeolite contact mass may also be enhanced by the introduction of magnesium oxide or oxides of the rare earth metals by base exchange. Another modification consists in leaching the zeolite with dilute acids removing part or all of the exchangeable alkali. The leach 'ing may be effected by treating the zeolite after hydration with 13% nitric acid until the desired amount of alkali has been removed. The amount of nitric acid necessary can be readily determined by testing a sample of the zeolite.

Instead of using an aluminate as the metallate component of the contact mass, other metallates may be substituted, for example beryllate may replace part or all of the aluminate. Other metal oxides can be introduced by base exchange and may possess specific catalytic properties or be stabilizer promoters.

Where a high concentration of catalytically effective metal oxides, such as nickel oxide, are present either as diluents or embedded in the zeolite molecule, it is sometimes of advantage to treat the contact mass with compounds containing the radicalsof the metal acids of the and 6th groups of the periodic system in order to form the so-called salt-like bodies, thus, for example the diluted zeolite prepared as described above may be treated with 35% of nickel nitrate solution until a maximum of base exchange has taken place. After washing out the excess nickel nitrate the wet zeolite is treated with 590 parts of 1% ammonium vanadate solution, the solution being permitted to trickle over the zeolite on a filten The resulting product is a salt-like body and is a well stabilized contact mass for the hardening of oils.

Of course other nickel containing contact masses described in the foregoing examples may also be used for oil hardening.

An example of an oil hardening process is the following:-5-O liters of a linseed oil showing an iodine number or" 178 are mixed with 1 lzilo or" the contact mass described above, the contact mass being suspended in a fine state of division and then, after heating the oil to 250 (3., hydrogen is passed in with vigorous agitation. From time to time sar pies are taken out and tested for melting point. After 9-12 hours a sample should show a melting point of about 63 C. and an iodine number practically zero. The reaction may then be stopped and the fully hydrogenated linseed oil can be separated from the suspended contact mass in the usual manner. The hydrogenation is preferably effected in a circulatory process, the hydrogen being as free as possible from poisons, such as sulfur compounds. For this purpose hydrogen-containing gases which are preparedby passing water gas through the vapors of boiling mercury alloys such as lead or cadmium mercury alloys or forced through these hot liquid'alloy baths may be effectively used and shows a sati factory purity.

Other hydrogonations may be eiiected by means of the same contact mass. Thus, for example, esters of phthalic acid, such as dimethyi, dibutyl, or diainyl phthalates can be hydrogenated to the corresponding esters of hexahydrophthalic acid. Similarly, esters of benzoic or toluic acid can be hydrogenated to the corresponding hexahydro derivatives. Terpenes can also be hydrogenated at 180-200 C. in the vapor phase with an excess of hydrogen. 1

In the claims the term permutogenetic covers base exchange bodies, silicious or non-silicious, the products obtained by the acid leaching of these base exchangebodies and the salt-like bodies obtained by the reaction of these base exchange bodies with compounds the acid radicals of which are capable of reacting with the base exchange bodies to produce products which show most of the properties of salts. When used in the claims, the term permutogenetic will have no other meaning.

The term chemical, solid, non-specific, vapor phase catalyst used in the claims is intended to refer to the substances described in the specification as stabilizer promoters, that is to say to substances contained in'the contact mass which have catalytic activity but which are not specific hydrogenation catalysts under the r action conditions used. Such substances are compounds selected from the group consisting of splitting catalysts, dehydrogenation catalysts, oxidation catalysts, and mixed dehydration and hydrogenation catalysts, and it is understood that this term will have no other meaning.

What is claimed as new is:

1. A method of catalytically hydrogenating unsaturated non-nitrogenous organic compounds which. comprises causing them to react with hydrogen containing gases in the presence of a contact mass which when freshly prepared contains a permutogenetic body, at least one efiective catalytic component being present other than an exchangeable base.

2. A method of catalytically hydrogenating unsaturated non-nitrogenous organic compounds which comprises vaporizing them, mixing the vapors of hydrogen-containing gases and passing the mixture at an elevated temperature over a contact mass containing a permutogenetic body, at least one catalytically effective component being other than an exchangeable base.

3. A method of catalytically hydrogenating unsaturated non-nitrogenous organic compounds which comprises subjecting them to reaction with hydrogen-containing gases in the presence of a contact mass containing a permutogenetic body having at least one catalytically effective component other than an exchangeable base and also containing at least one chemical, solid, non-specific, vapor phase catalyst.

4. A method of catalytically hydrogenating unsaturated non-nitrogenous organic compounds which comprises subjecting them to reaction with hydrogen-containing gases in the presence of a contact mass containing a permutogenetic body having at least one catalytically efiective component other than an exchangeable base and containing at least one compound of an element included in the group alkali metals and alkaline earth metals and at least one chemical, solid, non-specific, vapor phase catalyst.

5. A method of catalytically hydrogenating unsaturated non-nitrogenous organic compounds which comprises causing them to react with hydrogen-containing gases in the presence of a contact mass containing a diluted permutogenetic body.

6. A method accordingto claim 5 in which at least a portion of the catalytically effective components are present in the form of diluents in the permutogenetic body.

7. A method according to claim 5 in which the diluted permutogenetic body contains chemical, solid, non-specific, vapor phase catalysts.

8. A method according to claim 5 in which the diluted permutogenetic body contains compounds of an element included in the group alkali metals and alkaline earth metals and chemical, solid, non-specific, vapor phase catalysts.

9. A method according to claim '5 in which the diluted permutogenetic body contains chemical, solid, non-specific, vapor phase catalysts in the form of diluents;

10. A method of catalytically hydrogenating non-nitrogenous aromatic compounds which comprises causing them to react with hydrogen containing gases in the presence of a contact mass containing a permutogenetic body, at least one catalytically efiective component being other than an exchangeable base.

11. A method of catalytically hydrogenating non-nitrogenous phenols which comprises causing them to react with hydrogen-containing gases in the presence of a contact mass containing a permutogenetic body having at least one catalytically active component other than an exchangeable base. 7

12. A method of catalytically hydrogenating unsaturated non-nitrogenous organic compounds 

